TWI376014B - Ruthenium layer formation for copper film deposition - Google Patents

Description

Γ376014 玖, DESCRIPTION OF THE INVENTION: TECHNICAL FIELD The present invention relates to a method of forming a noble metal layer, and more particularly to a method of forming a tantalum layer for a copper integrated circuit. [Prior Art] The second quarter micron multilayer metallization is one of the main technologies of the next generation ultra large integrated circuit (VLSI) and giant integrated circuit (ULSI) semiconductor devices. The multilayer interconnects that are dominant in this technology need to be filled with contacts, vias, traces, and other components formed in the high aspect ratio aperture. The reliable formation of these components is important for VLSI & ULSI and for subsequent enhancement of component density and quality on individual substrates and wafers. Because when the circuit density increases, the joints, 逡a. 茌 茌 points, guide holes, lines and other components and the dielectric material between them are wide Tangcheng people, bamboo visibility, the mouth may be reduced to less than about 25〇奈' and the thickness of the dielectric layer is still captured, and the sound is still unchanged. The W maintains a constant quality, which results in an increase in the aspect ratio of the part, that is, its 13⁄4 degree is not in the official order. The twist ratio is increased. Many of the conventional sinks, when the aspect ratio exceeds 6, 1昧, and 6.1, when the difficulty of filling the structure is greater than 10:1, it is even more difficult. Yangshan 1 Tian Bing is more powerful. Therefore, there has been a lot of effort in shaping your knife system with an aspect ratio of 6:1 or higher. "More...width-free, non-porous nanoscale junctions. *When the component width is reduced, the device current is usually kept increasing, which causes the current density of #$燹 or 1 of these components to increase. Because of the aluminum resistivity, excellent adhesion to most dielectric materials, and the ability to easily image low-purity forms, the element...h = high 3 Γ376014 In semiconductor devices, the conventional metal for vias and traces is formed. However, aluminum has a higher electrical resistivity than other conductive metals such as copper. Aluminum also undergoes electromigration, causing pores to form in the conductor. Copper and copper alloys have a lower resistivity than aluminum and, at the same time, have higher electromigration resistance than aluminum. These features are important to support high current densities and high device speeds in high-order integrated circuits. Copper also has good thermal conductivity. Thus, copper becomes a selective metal on the semiconductor substrate that fills the quarter-micron high aspect ratio interconnect components.

For example, noble metal films such as ίε, Shi, Ming, Zhen and keys can also be used as copper vias and underlying layers. These corrosion-resistant and oxidized precious metals can provide a smooth surface, followed by deposition of a copper seed layer thereon using, for example, an electrochemical plating (ECP) process.

Precious metals are typically deposited using a chemical vapor deposition (CVD) process or a physical vapor deposition (PVD) process. Unfortunately, precious metals deposited on high aspect ratio interconnect components using CVD and/or PVD processes generally have poor step coverage (e.g., depositing a layer of discontinuous material). Poor step coverage of the precious metal material layer may cause the copper seed layer deposited by subsequent ECP processes to become uneven. Accordingly, there is a need in the art for a method of depositing precious metals in high aspect ratio interconnect components with good step coverage. SUMMARY OF THE INVENTION The present invention is directed to a method of forming a precious metal layer that can be used for high aspect ratio interconnect components. The noble metal layer is formed using a cyclic deposition process such as 4 1376014 Atomic Layer Deposition (ALD). The cyclic deposition process comprises alternately adsorbing a noble metal-containing precursor and a reducing gas on a substrate structure. The noble metal-containing precursor adsorbed reacts with the adsorbed reducing gas to form a noble metal layer on the substrate. Suitable precious metals include, for example, ruthenium, osmium, drill, imprint, nickel, and bonds. The precious metal layer forming system is compatible with the integrated circuit process. In an integrated circuit process, the noble metal layer can serve as the lower layer of a copper layer in a copper interconnect. For such embodiments, a preferred process sequence includes providing a substrate having an interconnect pattern in one or more dielectric layers on the substrate. The interconnect pattern includes a barrier layer deposited isomorphously thereon. A layer of noble metal (e.g., tantalum) is deposited isomorphically on the barrier layer. The noble metal layer is deposited by a cyclic deposition process by alternately adsorbing a noble metal-containing layer and a reducing gas on the substrate. Subsequently, the steel interconnect is completed by depositing a copper seed layer on the precious metal layer and then filling the interconnect with a large piece of copper metal. In one embodiment, a method of forming a film on a substrate, comprising placing the substrate in a processing chamber, and sequentially chemically adsorbing a single layer of a ruthenium-containing compound and a reducing gas are provided Forming the ruthenium layer on the substrate to form a ruthenium layer on at least a portion of the substrate. In another embodiment, a method of forming a ruthenium layer on a substrate for an integrated circuit process is provided The method comprises: placing a substrate in a processing chamber, wherein the processing chamber is in fluid communication with a gas distribution system; the gas distribution system transports the ruthenium-containing compound to the processing chamber; and chemically adsorbing a ruthenium-containing layer On the substrate; a reducing gas is delivered from the gas distribution system to the processing chamber and the reducing gas is reacted with the ruthenium containing layer to form a ruthenium layer on the substrate. 5 1376014 In another embodiment, there is provided a method of forming a ruthenium-containing layer on a surface of a substrate, the method comprising: a) exposing a surface of the substrate to a ruthenium-containing compound to form a ruthenium on the surface of the substrate a layer; b) rinsing the chamber with a flushing gas; c) reacting a reducing gas with the ruthenium containing layer; and d) rinsing the chamber with a flushing gas. In another embodiment, a method of forming a germanium layer on a substrate, comprising: placing a substrate in a processing chamber, and sequentially adsorbing a single layer of a germanium-containing compound and a reducing gas in sequence A layer of germanium is formed on at least a portion of the substrate. The method further includes a processing chamber comprising a substrate support member mounted on the substrate; a chamber cover, the central portion of the chamber cover including a channel, and the chamber cover includes The passage extends to a bottom surface of the peripheral portion of the chamber cover, the bottom surface having a size substantially covering the substrate; one or more valves connected to the passage, one or more gas sources, the gas sources being connected to Each valve and a reaction zone are defined between the chamber cover and the substrate. The reaction zone is small in volume. In another embodiment, a method of forming a germanium layer on a substrate for an integrated circuit process is provided, the method comprising: placing a substrate in a processing chamber; exposing the substrate to a double 2,4-Dimethylpentadienyl), chemically adsorbing a ruthenium-containing layer on a substrate; rinsing the processing chamber; exposing the ruthenium-containing layer to a reagent; and reacting the reagent with the ruthenium-containing layer, To form a layer of germanium on the substrate. In another embodiment, a method of forming a germanium layer on a substrate for an integrated circuit process is provided, the method comprising: placing a substrate in a processing chamber; exposing the substrate to a reagent and a sequential pulse of a process gas containing bis(2,4-dimethylpenta -6 1376014 dienyl) hydrazine; rinsing the processing chamber between sequential pulses of reagents and process gases; and bis (2,4 - 2 Methylpentadienyl) is reduced to form a ruthenium layer on the substrate. In another embodiment, a method of forming a nail layer on a substrate for an integrated circuit process is provided, the method comprising: placing a substrate in a processing chamber; exposing the substrate to a reagent And a sequential pulse of a ruthenium-containing compound treatment gas selected from the group consisting of: tris(2,2,6,6-tetramethyl-3,5-heptanedionate) ruthenium, bis(2,4- Dimercapto pentadienyl) hydrazine, dicarbonyl pentadienyl hydrazine, hydrazine acetylacetonate, (2,4-dimethylpentadienyl) fluorene (cyclopentadienyl), bis (2, 2,6,6-tetradecyl-3,5-heptanedionate) ruthenium (1,5-cyclooctadiene), (2,4-didecylpentadienyl) fluorene (methylcyclopentane) Dienyl), (1,5-cyclooctadiene) anthracene (cyclopentadienyl), (1,5-cyclooctadiene) anthracene (fluorenylcyclopentadienyl), (1,5- Cyclooctadiene) oxime (ethylcyclopentadienyl), (2,4-dimethylpentadienyl)anthracene (ethylcyclopentadienyl), (2,4-dimethylpentane) Alkenyl) hydrazine (isopropylcyclopentadienyl), bis(indenyl, hydrazine-dimethyl1,3-tetramethyldiimide) hydrazine (1,5-cyclooctadiene), double (Ν , Ν-dimercapto 1,3-dimethyl bis-imido acid) hydrazine (1,5-cyclooctadiene), (6-C6H6) hydrazine (1,3-cyclohexadiene), double ( Allyl) hydrazine (1,5-cyclooctadiene), bis(1,1-dimercapto-2-aminoethoxy acid) hydrazine (1,5-cyclooctadiene), double (1 , 1-dimercapto-2-aminoethylamino acid) hydrazine (1,5-cyclooctadiene) and its derivatives and mixtures thereof; in the sequence of reagents and process gases Flushing the processing chamber; and reducing the cerium-containing compound to form a ruthenium on the substrate. [Embodiment] 7 1376014 FIG. 1 shows a cross-sectional view of a processing chamber 10 that can be used to perform an integrated circuit process in accordance with an embodiment of the present invention. The processing chamber 1A typically includes a substrate support bracket 48 for supporting a substrate (not shown). The substrate support bracket 48 is movable in the vertical direction within the processing chamber 10 by the displacement mechanism 48a. Depending on the particular process, the substrate can be heated to the desired temperature before or during deposition. For example, the substrate support bracket 48 can be heated using the built-in heating element 52A. The substrate support tray can be resistively added by the current of the two-AC power source 52 to the heating element 52a. The substrate (not shown) is then heated by the carrier 48. Alternatively, the substrate holder 48 may use a radiant heater such as a lamp (not shown) plus a rnn vh λ ritual bracket clock, /, when entering the milk cleavage - generation - is contained in the substrate, the field ' The conventional method of 'monitoring the temperature of the bracket 48. The amount of AC power source 52 is controlled to control the temperature of the substrate used to heat element 52A. The substrate temperature can be maintained or controlled for the desired temperature. St Μ is also used to evacuate the processing chamber 10 and maintain the pressure within the processing chamber 0. The process gas is drawn into the manifold 34 via the gas manifold 34. The system is positioned on the substrate support bracket 48. Gas The various treatments are from Guanxian to a gas panel (not shown), which controls and supplies the body to the processing chamber.

The gas s S controller (not properly - the appropriate control and adjustment of the body manifold 34 is performed by mass flow '') and a microprocessor controller 70. Gas Disambiguation 8 101376014 Tube 34 allows most of the process gas to be introduced and evenly distributed throughout the process chamber. Alternatively, the gas tube 34 can be heated as needed to prevent the reaction gas from condensing within the manifold. Gas manifold 34 includes a plurality of electronically controlled valves (not shown). The electronically controlled valves herein represent any control valve that can be flowed into the processing chamber 10 by a valve opening and closing cycle, which cycle is from about 0.01 to about 10 seconds. Preferably, it is from about 0.05 seconds to about 2 seconds, preferably from about 0.1 second to about 1 second. Microprocessor controller 70 can be any form of general purpose computer processing (CPU) that can be used to control various chamber and sub-processor industrial settings. The computer can also use any suitable memory, such as a random access memory, a read only memory, a floppy disk drive, a compact disk drive, a hard disk drive, or the like, or a remote digital storage device. Various support circuits can be connected to the CPU to support the processor in a conventional manner. The required software program can be stored in the memory or executed by the remote second CPU. Execute a software program to start processing a program or program. When executing software, the general purpose computer can be turned into a specific program brain that can control the operation of the chamber to perform chamber processing. For example, a software program can be used to accurately electronically control the activation of a valve for performing a processing sequence in accordance with the present invention. Or the software program can also be executed in hardware, as a specific application integrated circuit, other types of hardware implementation, or a combination of software or hardware. Figure 2 is a cross-sectional view of an embodiment of a chamber 80 that includes a gas distribution apparatus 130 for cyclic deposition, such as atomic layer deposition or rapid chemical phase deposition. The detailed description of the chamber 80 is based on the same method of the United States patents used by the same assignee. The electronic control unit or the air supply unit 9 Γ 376014. Please disclose the No. 20030079686 and the same assignee application in 2002. U.S. Patent Application Serial No. 1/281,79, entitled "A Gas Distribution Apparatus for Atomic Layer Deposition", which is incorporated herein by reference, is incorporated herein by reference. Layer deposition (ALD) and rapid chemical vapor deposition refer to the sequential injection of a reactant to deposit a thin layer on the substrate structure. The steps of re-injecting the reactants can be repeated to deposit a plurality of thin layers. Thereby forming a conformal layer of the desired thickness. The chamber 80 can also be adapted for other deposition techniques. The chamber 80 includes a chamber body 82 having a side wall 84 and a bottom portion 86. The slit valve in the chamber 80 88 provides an access opening such that the robotic arm (not shown) can be transported from chamber 80 and retrieved from substrate 90, which is, for example, a 200 mm or 30 mm semiconductor wafer or glass substrate. 'Substrate support 92 with substrate receiving surface 91 support substrate 90. Substrate support 92 The motor U4 is lifted up to lift and lower the substrate support member 92 and the substrate 9 mounted thereon. The lift plate 116 connected to the lift motor n is mounted into the chamber 80 and passes through the substrate. The member 92 can be lifted and lowered by the movable mounting pin 120. The pin 12 can lift and lower the substrate 90 on the surface of the substrate support member μ. The substrate support member 92 can include a vacuum chuck 'an electrostatic chuck, or a clamping ring. The substrate 9 is fixed to the substrate support 92 during processing. The substrate support 92 can be heated to heat the substrate 9 placed thereon. For example, the substrate support 92 can be used internally. The heating element (e.g., an electric resistance heater) is heated or heated using radiant heat (e.g., a heating lamp mounted on the substrate support Μ). A flushing ring 1 1 2 can be mounted on the substrate support 92 to define a rinsing channel. 1 2 4, the flushing channel 丨24 provides a flushing gas to the periphery of the 10 1376014 substrate 90 to prevent deposition thereon. A gas distribution device 130 is mounted on the chamber body 82 to provide gas ( For example, processing gas and/or flushing gas) to chamber 80. A vacuum The system 1 7 8 is in communication with an extraction passage 179 to evacuate any gas from the chamber 80 and assist in maintaining the desired pressure or desired pressure range within the pumping zone 166 of the chamber 80. In the example, the chambers shown in Figures 1 and 2 allow the process gas and/or flushing gas to enter the chamber 80 via the gas distribution device 130 in a manner perpendicular to the plane of the substrate 90. Thus, the substrate The surface of the 90 is symmetrically exposed to the gas to allow a uniform film layer to be formed on the substrate. The process gas contains a ruthenium-containing precursor in one pulse and a reducing gas in the other pulse. The chamber 80, depicted in Fig. 2, produces a uniform film than the chamber 10 shown in Fig. 1. At the same time, chamber 80 uses a smaller cycle time than processing chamber 10 because chamber 80 spends less time rinsing and less time before the wafer is doped to saturation than chamber 10. Less doping time is important because many cerium-containing compounds have inherent characteristics of lower vapor pressure. The low vapor pressure means that the amount of precursor contained in the charge gas per unit time and temperature is less, so more time is required to contain the ruthenium compound (for example, double) than the conventional precursor with high vapor pressure (for example, TiCl4). (2,4-Dimethylpentadienyl) ruthenium) to saturate the surface of the wafer. Therefore, the chamber 10 may be doped with the antimony-containing compound in about 1 second or less, and the chamber 80 may be doped with the same antimony-containing compound in about 0.2 second or less. In one embodiment, the gas distribution device 130 includes a chamber cover 132. The 11 1-376014 chamber cover 132 includes an expansion passage 134 and a bottom surface ι6 〇 extending from a central portion of the chamber cover 132 - the bottom surface 16 延伸 extends from the expansion passage 134 to the chamber cover The surrounding part of 132. The bottom surface ι6〇 is sized and shaped to entirely cover the substrate 90 disposed on the substrate support 92. The expansion passage 134 has gas inlets 136A, 136B to provide a flow of gas from two similar valves 142A, 142B. The gas streams exiting the valves 142A, 142B may be provided together and/or separately. In one architecture, 'valves 142A, 142B are connected to different reactive gas sources' but are preferably connected to the same source of flushing gas. For example, valve 142a is coupled to reactive gas source 138 and valve 1 42B is coupled to reactive gas source 139, while valves 142A, 142B are coupled to purge gas source 140. Each valve 142A, 142B includes a delivery line 143A, 143B (having a valve seat assembly 144A, 144B, respectively) and a flush line 145A, 145B (having a valve seat assembly 146A, 146B, respectively). The transfer lines 143A, 143B are in communication with the reactive gas sources 138, 139 and are in communication with the gas inlets 136A, 136B of the expansion passage 134. The valve seat assemblies 1 44 A, 144B of the transfer lines 143A, 143B control the flow of reactant gases from the reactive gas sources 138, 139 to the expansion channels 134. The flushing line 1 4 5 A, 1 4 5 B is in communication with the flushing gas source 1 4 0 and intersects the conveying lines 143A, 143B downstream of the valve seat assemblies 144A, 144B of the conveying lines 143A, 143B. The valve seat assemblies 146A, 146B of the flush lines 145A, 145B control the flow of flushing gas from the purge gas source 140 to the transfer lines 143 A, 143B. If a carrier gas is used to transport the reactant gases from the reactive gas sources 138, 139, it is preferred to use the same gas as the carrier gas and the flushing gas (i.e., using argon as the carrier gas and flushing gas). 12 1376014 Each valve seat assembly 144A, 144B, 146A, 146B can include a diaphragm and a valve seat. The diaphragm can be opened or closed in a biased manner or opened and closed in an actuated manner. The diaphragm can be pneumatic or electric. Examples of pneumatic valves include pneumatic valves available from Fujiken and Veriflow. An example of an electric valve includes an electric valve purchased by Fujiken. The program editing logic controllers 148A, 148B can be coupled to the valves 142A, 142B to control the diaphragms of the valve seat assemblies 144A, 144B ' 146A, 146B of the valves 142A, 142B. The pneumatic valve can also provide a gas pulse for a period of time as low as about 0.020 seconds. The electric valve can also provide a gas pulse for a period of time as low as about 0.005 seconds. Electric valves typically require the use of a drive that is connected between the valve and the program editing logic controller. Valves 142A, 142B may be unretained volume valves to allow flushing of reactant gases from delivery lines 143A, 143B when valve seat assemblies 144A, 144B are closed. For example, the flush lines 1 4 5 A, 1 4 5 B can be positioned adjacent the valve seat assemblies 144A, 144B of the transfer lines 143A, 143B. When the valve seat assembly 1 44A, 1 44B is closed, the flushing lines 1 45A, 1 45B can provide flushing gas to flush the delivery line 1 4 3 A, 1 4 3 B » In the illustrated embodiment, the flushing line 1 The 4 5 A, 1 4 5 B-series are positioned slightly away from the valve seat assemblies 144A, 144B of the delivery lines 143A, 143B such that when opened, the flushing gas is not directly delivered to the valve seat assemblies 1 44A, 1 44B. The no-retention volume valve used herein is defined as a valve with a small retention volume that is negligible (i.e., does not have to be completely free of residual volume). Each valve 142A' 142B can be adapted to provide a combined gas stream and/or individual gas streams of reactive gases 138, 139 and flushing gas 140. The person who refers to the valve 13 is supplied by the reaction gas 138 and the flushing gas 140 of the wide 142A. An example of a gas stream comprising a continuous stream of flushing gas from a flushing gas source i4 via a flushing tube 45A and a source of reactive gas from the source

And send the reaction gas pulse of i43A. The continuous flow of flushing gas can be borrowed, and the diaphragm of the seat assembly 146A between the wash line (4) A remains open. The reaction gas pulse from the reactive gas source 138 can be provided by a diaphragm of the valve seat assembly (4) eight of the closed delivery line 143A. An example of an individual gas stream of the reaction gas 138 and the flushing gas 140 provided by the valve 142A', the valve 142A' includes a flushing gas pulse from the flushing gas source 14 through the flushing B channel 1 4 5 A, and the reaction gas. The source 丨 3 8 is pulsed by the reaction gas of the transport official road 143A. The flushing gas pulse can be supplied by a diaphragm of the valve seat assembly 1 4 6 A of the opening and closing wheel line 1 4 5 A, and the reaction gas pulse from the reaction gas source 1 38 can be opened and closed by the valve of the conveying line 143A. A diaphragm of the seat assembly 144A is provided.

Delivery lines 143A, 143B of valves 14 2A, 142B may be coupled to gas inlets 136A, 136B via gas conduits 150A, 150B. The gas conduits 150A, 150B may be integral or separate from the valves 142A, 142B. In the aspect, the thresholds 142A, 142B are connected relatively close to the expansion passages 134 to reduce the delivery conduits 143A, 143B and the gas conduits 150A, 150B between the valves 14 2A, 14 2B and the gas inlets 136A, 136B. Necessary volume. In Fig. 2, the expansion channel 134 includes a channel 'having an inner diameter which is gradually increased from the upper portion 137 of the expansion channel 134 to the lower portion 135 of the expansion channel 134 adjacent the bottom surface WO of the cover I32. 14 Γ 376014 In a particular embodiment, the inner diameter of the expansion channel 134 suitable for processing a chamber of a 200 mm diameter substrate is about 0.2 吋 (0.5 1 cm) to about 1.0 above the expansion channel 134.吋 (2.5 4 cm), more preferably from about 0.3 吋 (0.76 cm) to about 0.9 吋 (2.29 cm), preferably from about 0.3 吋 (0.7 6 cm) to about 0.5 吋 (1 · 2 7 cm) And between the expansion channel 1 3 4 and the portion 1 3 5 are between about 0.5 吋 (1 · 2 7 cm) to about 3 _ 0 吋 (7 · 6 2 cm), more preferably about 0.75 吋(1.91 cm) to about 2.5 吋 (6.35 cm), preferably between about 1.1 吋 (2.79 吋) to about 2.0 吋 (5.08 cm). In another particular embodiment, the inner diameter of the expansion channel 134 suitable for processing a chamber of 300 mm diameter substrate is about 0.2 吋 (0.5 1 cm) to about 1.0 吋 (2.5) above the expansion channel 134. 4 cm), more preferably about 0.3 吋 (0.76 cm) to about 0.9 吋 (2.29 cm), preferably about 0.3 吋 (0 · 7 6 cm) to about 0 · 5 吋 (1 · 2 7 cm) Between; and for a 300 mm substrate, the portion 135 below the expansion channel 134 is between about 0.5 吋 (1.27 cm) to about 3.0 (7.62 cm), preferably 0.75 吋 (1.91 cm) to about 2 5 吋 (6 · 3 5 cm), preferably between about 1.2 吋 (3.0 5 吋) to about 2.2 吋 (5 · 5 9 cm). In general, the above dimensions can be applied to an expansion passage to provide a total gas flow of from about 500 seem to about 3000 seem. In other particular embodiments, the dimensions can be varied to allow a particular airflow to pass. In general, larger gas streams will require larger diameter expansion channels. In one embodiment, the expansion channel 134 can be a truncated cone (including a shape like a head cone). Regardless of whether the gas is supplied towards the wall of the 13 1376014 channel 1 3 4 or directly downward toward the substrate, as the gas stream flows through the expansion channel 134, the gas flow velocity is reduced due to the expansion of the gas. The reduced gas flow rate reduces the likelihood that the gas stream will blow off the reactants adsorbed on the surface of the substrate 90. Without wishing to be bound by theory, it is believed that the portion 135 above the expansion channel 134 to the lower portion 135 of the expansion channel 134 gradually increases the diameter of the expansion channel 134, which reduces the adiabatic expansion of the gas as it passes through the expansion channel 134. Control the temperature of the gas. For example, sudden adiabatic expansion of the gas entering the expansion passage 134 via the gas inlets 1 3 6 A, 1 3 6 B may cause a drop in gas temperature, which may cause condensation of the gas and formation of particulates. On the other hand, the adiabatic expansion of the gas in the gradually expanding passage 134 according to the embodiment of the present invention is small. Therefore, more heat can be transferred into and out of the gas, so the temperature of the gas can be easily controlled by controlling the ambient temperature of the gas (i.e., controlling the temperature of the chamber cover 132). The progressively expanding channel may comprise one or more tapered inner surfaces, such as a linear tapered surface, a concave surface, a convex surface, or a combination thereof, or one or more tapered inner surface portions (ie, a partial tapered portion and a partial non- Cone). In one embodiment, the gas inlets 136A, 136B are positioned adjacent the portion 137 above the expansion passage 134. In other embodiments, one or more gas inlets may be positioned between the upper portion 137 and the lower portion 135 along the length of the expansion channel 134. In Fig. 2, a control unit 180 such as a stylized personal computer, workstation computer or the like can be connected to the chamber 80 to control the processing conditions. For example, control unit 180 can be configured to control various process gases and purge gas streams from gas sources 138, 139, 140 by valves 142A, 142B at different stages of the substrate processing sequence. As shown, the control unit 180 includes a central processing unit (CPU) 182, a support circuit 184, and a memory 186 including associated control software 183. Control unit 180 can be any form of general purpose computer processor that can be industrially set to control various chambers and sub-processors. The CPU 182 can use any suitable memory, such as a random access memory, a read only memory, a floppy disk drive, a compact disk drive, a hard disk drive, or any other form of digital storage, whether local or remote. . Various support circuits can be connected to the CPU 1 82 to support the chamber 100. Control unit 180 can also be coupled to another controller that locates program editing logic controllers 148A, 148B adjacent to individual chamber components, such as valves 142A, 142B. The two-way communication between the control unit 180 and various other components of the chamber 80 is handled by a plurality of signal cables, which are collectively referred to as a signal bus 188, some of which are shown in FIG. . In addition to controlling the process gas and flushing gas from the gas sources 1 3 8 , 1 3 9 , 1 40 via the program editing logic controllers 1 4 8 A, 1 4 8 B of the valves 142A, 142B, the control unit 1 800 can also The architecture is responsible for the automatic control of other activities for wafer processing, such as wafer transport, temperature control, chamber pumping, etc., some of which are explained as forming a precious metal layer below which will be used for high aspect ratio interconnects. A method of forming a precious metal layer of a component. The precious metal layer is deposited using a cyclic deposition process. The cycle 17 Γ 376014 deposition system comprises alternately adsorbing a precursor containing precious metal and a reducing body on a substrate structure. The pre-existing precious metal prey fish 1 is treated with a raw gas to form a metal layer on the substrate. The main body of winter, Tianbei metal can contain, for example, bismuth, palladium, platinum, cobalt 'nickel' and bismuth, etc. The tantalum layer has a thickness of less than 500 angstroms, preferably from about 10 angstroms to about 1 angstrom, preferably about 30 angstroms. Figure 3 illustrates a processing sequence 1 〇〇 which illustrates the various steps used to deposit the germanium layer. These steps can be performed in a process chamber similar to that described above with reference to Figures 1 and 2. As in the step, the substrate is supplied to the processing chamber. The substrate can be, for example, an enamel substrate having an interconnect pattern defined in a plurality of dielectric layers of material formed on the tantalum substrate. The processing chamber conditions, e.g., temperature and pressure, are adjusted to promote adsorption of the process gas onto the substrate' to promote the reaction of the noble metal precursor (e.g., monopentamethylene) and the reducing gas. In general, the substrate should be maintained below about 500 for precious metal layer deposition. (:, preferably in the range of from about 2 Torr to about 400 ° C, more preferably about 35 Torr). The processing chamber pressure is maintained in the range of from about Torr to about 80 Torr, preferably about The range from 1 Torr to about 1 Torr. The noble metal precursor can be supplied at a flow rate of about 〇iSccm to about 2 〇sccm, preferably about sclsccm to about 5sccm and more about 0'lsccm. Up to about 1 sccm. The reducing gas may be supplied at a flow rate of from about 1 sccm to about 10 〇 sccm, preferably from about 1 〇 sccm to about 50 sccm. In one embodiment where a constant carrier gas flow is required, as shown in step 104 A carrier gas flow is established within the chamber. A suitable carrier gas may be used to simultaneously act as a flushing gas 18 1376014 for processing the chamber to remove volatile reactants and/or by-products. For example, helium (He), argon (A) may be used. a carrier gas or a flushing gas such as nitrogen (Νη, - /ττ, 2), H (Η2), and combinations thereof. The flushing gas pulse is held for a predetermined period of time, for example, from about 0.1 to about 1 second. The range of seconds is about 0_07 seconds to about 2 seconds, more preferably about 1 second to about 1 second. It can be " about 500sccm to about 5000SCCm The flow rate between the carrier gas and the flushing gas is preferably about 500 sccm to about 2500 sccm for a 200 mm substrate and about 10 〇〇 sccm to about 5000 sccm for a 300 mm substrate. Referring to step 1 06, The carrier gas flow is established after the processing chamber of the second and second processing chambers. A pulse containing the shellfish is added to the carrier gas flow - the vocabulary...1 in the processing chamber or carrier gas flow. Preferably, the pulse of the precursor is for a predetermined period of time, for example: quality; containing a range of about 1 sec., preferably A is about 0·0 1 to live in Mayo. 0 5 seconds to 0.1 seconds Up to about 1 second, β ^ 1 · 5 seconds containing noble metal precursors to contain precious metals such as ruthenium, osmium, etc. 、, platinum, cobalt, nickel, appropriate yttrium-containing precursors include: tri-acid 钌Bis(2,4-dimethylpentane: 2'6'6·tetrahyl- 3,5-heptanedione acetophenone pyruvate, (2,4-dimethyl, ruthenium), dicarbonyl Pentadienyl ruthenium, (2,2,6'6-tetramethyl-3,5-glycolide-di-diyl)-shu (cyclopentadienyl), bismethylpentadienyl) Base ring 黾) 钌 (1,5-cyclooctadiene), (2, 4·dipentadienyl)'(ls5_cyclooctadienyl), (1,5·cyclooctadiene)indole (cyclooctadiene)钌 (ethylcyclopentadiene) Cyclopentadienyl), (1,5-cyclopentadienyl), (2,4-dimethyl)(2,4-dimethylpentadienyl)anthracene (ethyl), three ( 2,2,6,6, tetramethyl-3-ylpentadienyl) guanidine (isopropylcyclopentadiene, 'glydione acid) nail, bis (Ν, Ν-dif group 19 1376014 1, 3-tetramethyldimethylene imidate) bismuth (1,5-cyclooctadiene) 'bis(乂>|_dimethyl 1,3 - fluorenyl-i-imino) nail (1, 5 - cyclooctane bake), bis (dipropyl) hydrazine (1,5-cyclooctane dilute) '(776-C6H6) 钌 (ι, 3-cyclohexadiene), double (! , bis-indenyl-2-aminoethoxy acid) hydrazine (1,5-cyclooctadiene), bisdimethyl-2-ethylaminoethyl amide) ruthenium (1,5-cyclooctane Dilute) and its derivatives and mixtures thereof. Suitable palladium-containing precursors include: bis(allyl)palladium, bis(2-methylallyl)palladium and (cyclopentadienyl)(allyl) Palladium and so on. Suitable platinum-containing precursors include: dimethyl (cyclooctadiene) platinum, trimethyl (cyclodienyl) platinum trimethyl (decylcyclopentadienyl) platinum, cyclopentadienyl (ene) Propyl)platinum, methyl (carbonyl)cyclopentadienyl platinum, trimethyl(acetonitrile)platinum, and bis(acetylpyruvyl)platinum and the like. Suitable cobalt-containing precursors include: bis(cyclopentadienyl)cobalt, (cyclopentadienyl)(cyclohexadienyl)cobalt,cyclopentadienyl(1,3-hexadienyl)cobalt, (cyclobutadienyl)(cyclopentadienyl)cobalt, bis(methylcyclopentadienyl)cobalt, (cyclopentadienyl)(5-methylcyclopentadienyl)cobalt and bis( Ethylene pentylcyclopentadienyl) cobalt and the like. Suitable nickel-containing precursors include bis(methylcyclopentenyl) nickel and the like. Suitable ruthenium-containing precursors include: bis(carbonyl)(cyclopentadienyl)anthracene, bis(propylene)anthracene, bis(carbonylethylcyclopentadienyl)anthracene and bis(mono)(methylcyclopentane) Alkenyl) 铑. The pulse period of the precursor containing the precious metal depends on several factors such as the volume of the processing chamber used, the vacuum system to which it is connected, and the volatility/reactivity of the reactants used. For example, (1) large volume processing chambers may take longer to stabilize processing conditions such as carrier gas/flush gas flow and temperature, thus requiring longer pulse times; (2) lower process gas flow rates are also required Longer time to stabilize the processing conditions, so a longer pulse of 20 Γ 376,014 times is required; and (3) lower chamber pressure is not processed, so a longer pulse time is required. Generally two

The condition is such that the noble metal contained therein is a pulsating substance, so that at least the single layer contains the precursor of the genus Besinium, and then remains in the chamber, and the excess contains the precious metal carrier gas.纟2 is a period in which the reducing gas pulse continues for a predetermined period of the original gas pulse by the processing chamber in step 108 after the excess of the precious metal gas stream is flushed out of the processing chamber. It should be long enough to adsorb the body on the precursor containing the precious metal. The reducing gas time is, for example, from about 01.01 second to 10 seconds to about 2 seconds, more preferably from about 〇.1 second to about 丨 second. The body is flushed out of the processing chamber by the carrier gas stream. Appropriate reduction _ such as A or atom H), ammonia (Nh 〇, decane (siH4) trioxane (Si3H8), tetraoxane (Si4Hi〇), dimercapto-based sulphur (SiCH6), ethyl decane (SiC2H8), gas Chloroquinone (Cl2SlH3), hexa-dioxane (Si2Cl6), borane, tetraborane, pentaborane, triethylborane, compound. Steps 104 to 108 include the deposition of a precious metal. For this embodiment Providing a constant carrier gas alternate pulse period and non-pulse period modulation. The constant carrier gas flow alternately contains a noble L in the pulse period, and is discharged from the processing chamber to provide a sufficient amount to provide a sufficient amount before being driven. Adsorbed on the substrate. The insulator is added to the carrier gas stream by a constant removal of β. In general, at least a single layer of reducing gas pulse continues for a predetermined period of time. After about 1 second, the 'excessive reducing gas I body may contain hydrogen (for example, dioxane (Si2H6), k decane (SiC2H6), formane (ClSiH3), two sheds, two sheds, three derivatives thereof And an implementation of the cycle of its group flow to the processing chamber to fix the carrier gas The constant metal precursor and the 21 1376014 raw gas, and only the carrier gas flow in the non-pulsing period. Each of the noble metal precursor pulse and the reducing gas pulse can last for the same time. The duration of the object pulse may be the same as the duration of the reducing gas pulse. For this embodiment, the period of time during which the noble metal precursor pulse is contained (τ〇 is equal to the period of the reducing gas pulse (τ2). Or 'each The noble metal precursor pulse and the reducing gas pulse may last for different times, ie, the duration of the precious metal precursor pulse may be shorter or longer than the duration for the reducing gas pulse. For this embodiment, the inclusion The period of the precursor pulse of the noble metal is different from the period of the reducing gas pulse (τ2). In addition, the non-pulsing period between the pulse of the precursor and the pulse of the reducing gas before each precious metal is contained may also last for the same time. a non-pulsing period between the precursor pulse and each reducing gas pulse before each noble metal is contained

The chamber. Or, before each precious metal contains a precursor pulse and a reducing gas pulse

Non-pulse period between precursor pulses. . For this embodiment, the inclusion 22 1376014 (T3) is different from the non-pulsing period (Τ 4) of the time at which the reducing gas pulse and the precious gold pulse are contained. Prior to the non-pulse period two, the object pulse beta gas stream is provided to the processing chamber. /, has a value; | In addition, for each deposition cycle, each contains & pulse, reducing gas pulse and the non-pulp bimetallic precursor between them... This example, before containing precious metals: two continued When the time is the same (Τι), the time period (Τ2) of the wind body pulse is reduced, and the inner interval is included.

Non-pulsing time period between the pulse of the rushing and reducing gas (5) and = pulsing of the pulse of the material per ^^ Γ (4) Non-pulse period between the pulses (TO for the middle, containing the S ' ' 儿 环 环 (C,) ring ( C2 C: The time period of the pulse of the precursor (5) is the same as the subsequent deposition cycle:::: the period of the precursor pulse of the noble metal (5) The continuous pulse disk is in the first deposition cycle (C1), each reducing gas Reducing (4) pulses and the same in each non-pulse time between the precursor of the precious metal and the reducing gas (C2~cn) Pulse period lasts

In one of the shell metal deposition processes or in the majority of the deposition cycle, the charge pulse, the reducing gas pulse and the non-pulse between them are at least _π, 1 for different durations. For the period of time (Τ) of the pulse of the precursor of the three or three internal metals, the gas pulse 睥Μ & ^ reduction ^ 曰Ί 曰Ί section (D 2), containing precious metal precursors Pulse and milk pulse, the north β “term, non-pulse period (Τ'3) and reducing gas and the precious gold containing 23 Γ376014, the non-pulse between the pulses of the precursor is called the middle section (1%) In the cyclic deposition process—or most of the deposition cycle—the right octet has different values. For example, in the first deposition cycle (C丨), the period of the noble metal-containing precursor pulse can be longer or shorter. In the subsequent deposition cycle]) ▲ The compensation ring (C2 Cn) contains one of the pulse pulses or most of the time (0. Similarly, in the first deposition cycle (C丨) The duration of the pulse of the reducing gas pulse and the non-contact between the pulse of the noble metal and the reducing gas pulse can be different from the reduction in the subsequent deposition cycle (C2.._Cn). Long-lasting original rolling body pulse duration, containing metal precursors and reducing gases Non-pulse time between pulses ^ and: test step η η. 'In each - deposition cycle (....: a good degree of precious metal will be formed on the substrate. Take) can then need a subsequent deposition cycle to reach the water , thickness. ® This, repeat steps 104 to 108 until the required thickness is completed. The j, eF, M genus layer. Then, when the precious metal layer of the desired thickness is formed, as in step Shao 112 The system is stopped. In another process as described in Fig. 4, the deposition of the poor layer of the mussels includes individual impregnations of precious metal precursors, reducing gases and flushing gases. For this example - 13⁄4 precious metal The layer deposition sequence 2〇〇 includes, a substrate is supplied to the processing chamber (step 202), and the rocking plate is depleted, such as a rinsing gas for the first pulse to the processing chamber (step 204), provided within the pulse The shell metal precursor is directed to the processing chamber (step 206), providing a second pulse/r condition gas to the processing chamber (step 208), providing a reducing gas pulse to the processing chamber, step 210), and then depending on whether The required thickness is only 'm layer (step 212)' Repeat steps 2〇4 to 210 or stop the deposition process (step 214) 〇24 Γ376014 As discussed above with reference to Figure 3, each of the reducing gas and the rinsing gas before the precious metal is contained: a period of one pulse may have For the same duration, or in the 'precious metal deposition process, the relevant time period for the precursor, reducing gas, and rinsing one or more pulses in the one or more cycles may have different durations in Section 3-4 ® The middle metal deposition cycle is depicted as starting with a metal squid pulse and then providing a pulse of reducing gas. The shell metal layer > the gas accumulation cycle can begin with a pulse of reducing gas and then contain a noble metal precursor pulse. In an exemplary process, a sub-layer deposition process of the processing chamber 80 of FIG. 2 deposits a layer of germanium on a substrate (eg, 3 〇〇mm), a gas source 138, from about 0.01 cmcm to about 5 sccm. Preferably, about (a flow rate to about 1 sccm provides a pulse of a ruthenium containing compound such as bis(2,4-di-diethyl) ruthenium via a valve 1 4 2 a, due to the comparison of the reaction zone 164 (compared to the first The chamber of the figure 8) has a pulse duration of about 1.25 less 'e.g. about 0.1 second or less, and as low as about 〇. 〇 5 seconds or less of dibrane (BZH6) reducing gas pulse can be gas The flow rate of the source 139 lsccm to about 80 sccm, preferably from about 1 〇sccm to about the flow rate 'via valve 1 42B, lasts about 2 seconds or less, about 1 second side or 0.1 second or less, due to The small volume of argon purge gas from reaction zone 164 is maintained at a flow rate between about 500 sccm and about 5000 sccm, and between 1500 sccm and about 3,500 sccm, continuously supplied by gas source through valve 142 VIII, 1428. The time between 2,4-dimethylpentadienyl)B2H6 pulses may be about 0.5 seconds or less, for example, about ruthenium, the same or not most of the gas is expensive. Who provided the original inner comprising: a) .1 seem small volume methylpentyl seconds or less. For example, take about 5 Oseem, less, so. A better than about 140 pulses and .1 seconds or 25 1376014 are less, and as low as 0.07 seconds or less due to the volume of the reaction zone 164. It is believed that with a reactant gas and/or a flushing gas, a pulse time of 0.016 seconds is sufficient to fill the reaction zone, and for a reaction zone 164 for a wafer (eg, 200 mm), a shorter pulse time is used. Preferably, it is maintained between about 200 ° C and about 400 ° C. The chamber pressure is between about 1.00 and about 10 Torr, preferably about 4 Torr, per cycle. A reproducible process having a thickness of from about 0.5 angstroms to about 1.0 angstroms is provided until the desired thickness is achieved. In one embodiment, the tantalum layer is deposited as a side cover of about 50 angstroms or less. In another embodiment, the tantalum layer is deposited to a coverage of about 20 angstroms or less. In another embodiment, the tantalum layer is deposited in a wall coverage of about 10 angstroms or less. A layer having a thickness of about 10 angstroms or less is sufficient in this case as an underlying layer of copper deposition (i.e., seed layer) and prevents copper from expanding:) barrier layer). In one aspect, a thin underlayer may be used to facilitate filling of sub-micron (e.g., less than 0.15 micron) and smaller features of high aspect ratio, and sidewall cladding having greater than 50 angstroms may also be used. In one real, helium is deposited as a layer. In another embodiment, the germanium is deposited with a barrier layer. Formation of copper interconnects Fig. 5A-5C shows a cross-sectional view of the substrate at various stages of the process of adding the precious metal layer of the present invention. For example, Figure 5A shows a cross-sectional view of 300 with metal contacts 304 and dielectric layer 302 formed on the 300. Substrate 300 may comprise, for example, ruthenium, osmium or gallium arsenide as small as about less. Add a good ear. Floor. The side of the wall covering side wall is considered to have "that is, when the embodiment is a connecting substrate substrate semi-conducting 26 1376014 body material. The dielectric layer 302 may comprise an insulating material such as yttria-nitride or the like. The metal contact 304 may Copper or the like is included. The aperture 304H can be defined in the dielectric 302 to provide an opening on the metal contact 304 to define 304H in the dielectric layer 302 using conventional lithography and etching techniques. A barrier layer 306 can be formed in the definition In 304H of the electrical layer 302. The barrier layer 306 may comprise one or more of a metal containing a rich metal such as titanium, nitride, group, nitride, cast and II, etc. For example, titanium tetrachloride is used. A titanium oxide chemical vapor deposition (CVD) ALD process is used to deposit titanium nitride. Referring to Figure 5B, a noble metal layer 3 0 8 (e.g., germanium) is formed on layer 306. The noble metal layer uses the third The cycle technique of Figure 4 is formed. The thickness of the precious metal layer varies depending on the structure to be fabricated. Typically, the thickness of the precious metal layer is less than 1 Å and is between about 10 angstroms and about 60 angstroms. In one embodiment, a layer of about 30 angstroms Thickness. Subsequently, referring to Figure 5C, the aperture 3 04H can be filled with copper 3 to complete the copper interconnect. The copper 310 can be formed using one or more suitable depositions. In one embodiment, for example, a CVD process can be used. A layer is formed on the tantalum layer, followed by an electrochemical plating (ECP) process to deposit the master to fill the interconnect. In another embodiment, a copper seed layer is deposited by phase deposition (PVD), followed by Electroless copper plating is used to deposit the host filler. In another embodiment, the germanium layer acts as a seed layer on which EPC or electroless plating is performed to deposit a copper host filler. Or the barrier deposition device preferably has 10, the process copper seed copper liquefaction gas-copper directly 27 1376014 performs several integration procedures to form a layer in the interconnect. In an embodiment, the subsequent steps are: a) Pre-cleaning the substrate; barrier layer (eg, TaN deposited by ALD); c) depositing ALD with ALD: and depositing copper in the form of ECp or Cu-PVD followed by ECP. In another embodiment, the subsequent steps include: a) Depositing a barrier layer (eg ALD _ TaN); b) a hole step; Ο depositing the nail with ALD; and d) depositing copper in the manner of ECP or cu_pvD followed by ECP. In another embodiment, the subsequent steps include: 3) depositing ruthenium with ald; b) punching step; c) ALD deposition 钌; and d) depositing copper in the manner of ECp or Cu-PVD followed by ECP. In a further embodiment the subsequent steps comprise: a) depositing ruthenium by ALD; b) a punching step; and depositing ruthenium by ALD; d) depositing copper with ECP. In another embodiment, the subsequent steps comprise: a) pre-cleaning the substrate; b) depositing ruthenium in ALD; and c) depositing copper in the manner of EcP or Cu_PvD followed by ECP. The pre-cleaning step involves a method of cleaning or purifying the vias, such as removing residues (e.g., carbon) at the bottom of the vias or reducing the oxidized steel to copper metal. The punching step includes a method of removing material (e.g., a barrier layer) from the bottom of the via hole to expose the conductor layer (e.g., copper). Further disclosure of the puncturing step is described in the U.S. Patent No. The punching step is performed in a processing chamber, such as a barrier chamber or a cleaning chamber. In an embodiment of the invention, the cleaning step and the punching step are applied to the barrier layer. Further disclosure of the holistic method is illustrated by the same assignee application dated June 13, 2003, the integration of tantalum nitride ALD for steel metallization, U.S. Provisional Application No. 6/47 8,663 In the number, the case is incorporated by reference. 28 1376014 Although the foregoing is directed to the preferred embodiments of the present invention, other embodiments of the present invention may be devised without departing from the scope of the invention, and the scope of the invention is determined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS The foregoing detailed description of the preferred embodiments of the invention may be However, it is to be noted that the appended drawings are merely illustrative of the invention and are not to be construed as limiting 1 is a cross-sectional view of a chamber that can be used to perform the cyclic deposition process of the present invention; FIG. 2 is a cross-sectional view of another chamber that can be used to perform the cyclic deposition process of the present invention; Process for recycling a precious metal layer of a cyclic deposition according to an embodiment; FIG. 4 is a view showing a process of using a noble metal according to another embodiment of the present invention; and FIG. 5A-5C is a profile of an integrated circuit process Figure. [Main component symbol description] Do not enter one 〇 (that is, additional implementation of the allowable cavity a technical accumulation 10 processing chamber 18 vacuum pump 34 gas manifold 48 bracket 29 1376014 48A displacement mechanism 50 Α temperature sensor 52 AC power 52 Α Heating Element 70 Microprocessor Controller 80 Chamber 82 Chamber Body 84 Side Wall 86 Bottom 88 Slit Valve 90 Substrate 91 Receiving Surface 92 Support 114 Lifting Motor 116 Lifting Plate 118 Lifting Motor 120 Pin 122 Flushing Ring 124 Flushing Channel 130 Gas distribution device 132 chamber cover 134 expansion channel 135 lower portion 137 upper portion 136A, B gas inlet 138 reactant gas source 139 reactant gas source 140 flushing gas source 142A, B valve 143 Α > Β gas distribution line 1 4 4 A, B Seat Assembly 1 4 5 A, 冲洗 Flush Line 1 4 6 A, B Seat Assembly 150A, B Gas Line 160 Bottom 166 Pumping Area 178 Vacuum System 179 Pumping Channel 180 Control Unit 182 Central Processing Unit 183 Control Software 184 Support Circuit 186 Memory 300 Substrate 302 Dielectric Layer 304 Metal Contact 3 0 4 Η Aperture 306 Barrier Layer

30 1376014 308 precious metal layer 3 10 copper

31

Claims (1)

1376014 Picking up, patent application scope: 1. A method for forming a film on a substrate, the package 1 is placed in a processing chamber, where a gas distribution device has an expansion a channel, the substrate is exposed to a processing gas, the processing gas compound or a reducing gas; the processing gas is transported by the expansion channel; and the substrate is sequentially exposed to the compound in an atomic layer deposition process And the reducing gas to be at least one layer of the substrate. 2. The method of claim 1, wherein the washing chamber flushes the processing chamber and performs the atomic layer deposition cycle, the deposition cycle comprising sequentially transporting the cerium-containing compound body, the reducing gas, and the rinsing Gas to the processing chamber 3. As in the method of claim 2, the compound is selected from the group consisting of (2,2,6,6-tetramethyl-3,5- Hexanedione acid) bismuth, bis(2,4-difluorene, dicarbonylpentadienyl hydrazine, hydrazine acetonate, (2,4-alkenyl)anthracene (cyclopentadienyl), bis ( 2,2,6,6-tetramethyl-3,5 fluorene (1,5-cyclooctadiene), (2,4-didecylpentadienyl) fluorene (methyl), (1,5 -cyclooctadiene) fluorene (cyclopentadienyl), (1,5-cyclooctyl) the following steps: the chamber contains the expansion flux comprising a deuterium containing the deuterium to form one of the components One of the strokes is deposited, the rinse gas containing the ruthenium, including: trisylpentadienyl) dimethylpentane-heptanedionate)cyclopentadienyldiene) (32 Γ376014) Dienyl), (1,5-cyclooctane Alkenyl (ethylcyclopentadienyl), (2,4-dimethylpentadienyl)anthracene (ethylcyclopentadienyl), (2,4-dimethylpentadienyl) Anthracene (isopropylcyclopentadienyl), bis(N,N-dimercapto1,3-1,3-dimethyldiimide) hydrazine (1,5-cyclooctadiene), bis(Ν, Ν-dimercapto1,3-1,3-dimethylimidazolium) nail (1,5-cyclooctadiene), bis(allyl)indole (1,5-cyclooctadiene), (t ?6-C6H6) 钌(1,3-cyclohexadiene), bis(1,1-dimethyl-2-aminoethoxy) hydrazine (1,5-cyclooctadiene), double (1 , 1-dimethyl-2-aminoethylamino acid) hydrazine (1,5-cyclooctadiene) and derivatives thereof and mixtures thereof. 4. The method of claim 3, wherein the reducing gas comprises one or more gases selected from the group consisting of hydrogen, ammonia, decane, dioxane, dinonyl decane, decyl decane, ethyl decane, A group consisting of chlorodecane, dichlorodecane, hexa-dioxane, borane, diborane, triborane, tetraborane, pentaborane, triethylborane, and combinations thereof. 5. The method of claim 4, wherein the step of forming the layer of tantalum is carried out at a temperature ranging from about 200 °C to about 400 °C. 6. The method of claim 4, wherein the step of forming the layer of tantalum is carried out at a pressure of from about 0.1 Torr to about 80 Torr. 7. The method of claim 2, wherein the flushing gas system comprises 33 1376014 selected from the group consisting of helium, argon, hydrogen, nitrogen, and combinations thereof. 8. The method of claim 6, wherein the ruthenium containing compound is pulsed into the processing chamber for from about 0.05 seconds to about 1.5 seconds. 9. The method of claim 8, wherein the reducing gas system enters the processing chamber in a pulsed manner for about 1 second to about 2 seconds. 10. The method of claim 7, wherein the flushing gas system enters the processing chamber in a pulsed manner for about 0.07 seconds to about 1 second. 0. The method wherein the tantalum layer has a thickness of from about 10 angstroms to about 100 angstroms. 12. The method of claim 1, wherein the process gas system is delivered in a vertical manner relative to a plane of the substrate. 13. A method for forming a layer of germanium on a substrate in an integrated circuit process, comprising the steps of: placing the substrate in a processing chamber, wherein the processing chamber is associated with a gas distribution The system is in fluid communication, the gas distribution system having a central expansion channel; 34 1376014 from the gas distribution system to deliver a ruthenium containing compound to the processing chamber, wherein the ruthenium containing compound is from the central expansion channel relative to the substrate a plane is conveyed in a vertical flow; a chemical adsorption of a ruthenium containing layer to the substrate; a reducing gas is delivered from the gas distribution system to the processing chamber; and the reducing gas is reacted with the ruthenium containing layer, To form the nail layer on the substrate. 14. The method of claim 13, wherein the processing chamber is flushed with a flushing gas before and after the reducing gas is delivered. 15. The method of claim 14, wherein the cerium-containing compound is selected from the group consisting of tris(2,2,6,6-tetramethyl-3,5-g Diketo acid) bismuth, bis(2,4-dimethylpentadienyl) fluorene, dicarbonyl pentadienyl hydrazine, hydrazine acetylacetonate, (2,4-didecylpentadienyl) fluorene (cyclopentadienyl), bis(2,2,6,6-tetramethyl-3,5-heptanedionate) ruthenium (1,5-cyclooctadiene), (2,4-di (Pentapentadienyl) fluorene (methylcyclopentadienyl), (1,5-cyclooctadiene) fluorene (cyclopentadienyl), (1,5-cyclooctadiene) fluorene (methyl) Cyclopentadienyl), (1,5-cyclooctadiene) anthracene (ethylcyclopentadienyl), (2,4-dimethylpentadienyl)anthracene (ethylcyclopentadienyl) ), (2,4-dimethylpentadienyl)anthracene (isopropylcyclopentadienyl), bis(indenyl, fluorenyl-dimercapto1,3-1,3-diyl imienoic acid) (1,5-cyclooctadiene), bis(indenyl, fluorenyl-dimercapto1,3-1,3-dimethylimidazolium) hydrazine (1,5-cyclooctadiene), bis(allyl) ) 钌 (1,5-cyclooctane II 1376014 ene), (77 6-C6H6) 钌(1,3-cyclohexadiene), bis(1,b-dimethyl-2-aminoethoxy)indole (1,5-cyclooctadiene), bis(1,1-didecyl- 2-Aminoethylamino acid) hydrazine (1,5-cyclooctadiene), and derivatives thereof, and mixtures thereof. 16. The method of claim 15, wherein the reducing gas comprises one or more gases selected from the group consisting of hydrogen, ammonia, decane, dioxane, dinonyl decane, methyl decane, ethyl decane. a group consisting of chlorodecane, dichlorodecane, hexachlorodioxane, borane, diborane, triborane, tetralkane, pentaborane, triethylborane, and combinations thereof. 17. The method of claim 16, wherein the step of forming the layer of tantalum is carried out at a temperature of from about 200 ° C to about 400 ° C. 18. The method of claim 16, wherein the step of forming the layer of tantalum is carried out at a pressure of from about 0.1 Torr to about 80 Torr. The method of claim 14, wherein the flushing gas system is selected from the group consisting of helium, argon, hydrogen, nitrogen, and combinations thereof. The method of claim 18, wherein the ruthenium-containing compound enters the processing chamber in a pulsed manner for from about 0.05 seconds to about 1.5 seconds. The method of claim 20, wherein the reducing gas system enters the processing chamber in a pulsed manner for from about 0.1 second to about 2 seconds. 2. The method of claim 19, wherein the flushing gas system enters the processing chamber in a pulsed manner for from about 0.07 seconds to about one second. 23. The method of claim 16, wherein the layer of tantalum has a thickness of from about 10 angstroms to about 100 angstroms. 24. A method of forming a layer comprising tantalum on a substrate in a processing chamber, comprising the steps of: a) exposing the surface of the substrate to a germanium containing compound to form a germanium containing layer on the surface of the substrate The sulphate-containing compound is delivered by a gas distribution system having a central expansion channel; b) rinsing the processing chamber with a flushing gas; c) delivering a reducing gas from the central expansion channel to cause the reducing gas to The ruthenium containing reaction; and d) rinsing the processing chamber with the flushing gas. 25. The method of claim 24, wherein the layer 37 1376014 is formed by an ALD process cycle comprising repeating steps a) through d). 26. The method of claim 25, wherein the cerium-containing compound is selected from the group consisting of tris(2,2,6,6-tetraf-group-3,5-g Diketo acid) bismuth, bis(2,4-dimethylpentadienyl) fluorene, dicarbonyl pentadienyl hydrazine, hydrazine acetyl acetonate, (2,4-didecylpentadienyl) fluorene (cyclopentadienyl), bis(2,2,6,6-tetramethyl-3,5-heptanedionate) hydrazine (1,5-cyclooctadiene), (2,4-dimethyl (Pentapentadienyl) fluorene (methylcyclopentadienyl), (1,5-cyclooctadiene) fluorene (cyclopentadienyl), (1,5-cyclooctadiene) fluorene (fluorenyl) Cyclopentadienyl), (1,5-cyclooctadiene) anthracene (ethylcyclopentadienyl) '(2,4-dimethylpentadienyl)anthracene (ethylcyclopentadienyl) , (2,4-dimethylpentadienyl)anthracene (isopropylcyclopentadienyl), bis(N,N-dimethyl1,3-tetradecyldiimide) (1,5-cyclooctadiene), bis(N,N-dimercapto1,3-1,3-dimethylimidazolium) hydrazine (1,5-cyclooctadiene), bis(allyl) ) 钌 (1,5-cyclooctadiene), (7? 6-C6H6) 钌 (1,3- Hexadiene), bis(1,1-dimercapto-2-aminoethoxy)indole (1,5-cyclooctadiene), bis(1,1-dimethyl-2-amino group B Amino acid) hydrazine (1,5-cyclooctadiene), and derivatives thereof, and mixtures thereof. 27. The method of claim 26, wherein the reducing gas comprises one or more gases selected from the group consisting of hydrogen, ammonia, decane, dioxane, dinonyl decane, methyl decane, ethyl decane. a group of gas decane, dioxane, hexadioxane, borane, diborane, triborane, tetraborane, pentaborane, triethylborane, and combinations thereof. 38. The method of claim 27, wherein the step of forming the layer is carried out at a temperature between about 200 ° C and about 400 ° C. 29. The method of claim 27, wherein the step of forming the layer is performed between a pressure of from about 0.1 Torr to about 80 Torr. 30. The method of claim 25, wherein the flushing gas system is selected from the group consisting of helium, argon, hydrogen, nitrogen, and combinations thereof. 31. The method of claim 29, wherein the ruthenium containing compound is pulsed into the processing chamber for about 5 seconds to about 1.5 seconds. The method of claim 3, wherein the reducing gas system enters the processing chamber in a pulsed manner for from about 0.1 second to about 2 seconds. The method of claim 30, wherein the flushing gas system enters the processing chamber in a pulsed manner for from about 0.07 seconds to about one second. 39. The method of claim 27, wherein the steps a) to d) are repeated to form the ruthenium containing layer having a thickness of from about 10 angstroms to about 100 angstroms. 35. The method of claim 24, wherein the ruthenium containing compound is delivered in a perpendicular manner relative to a plane of the substrate. 36. A method of forming a layer of tantalum on a substrate, comprising: placing the substrate in a processing chamber, wherein the processing chamber comprises: a substrate support having the substrate; a chamber a cover having a central expansion passage in a central portion of the chamber cover, the chamber cover and a bottom surface extending from the central expansion passage to a peripheral portion of the chamber cover, the shape of the bottom surface The substrate may substantially cover the substrate; one or more valves connected to the central expansion channel; one or more gas sources connected to each valve; a reaction zone defined between the chamber cover and the substrate, the reaction zone comprising a small volume; and at least one of the monolayer containing a ruthenium compound and a reducing gas by sequential chemical adsorption The layer of germanium is formed on a portion. 3. The method of claim 36, wherein the processing chamber is flushed with a flushing gas after each single layer of chemisorption. 40. The method of claim 37, wherein the cerium-containing compound is selected from the group consisting of tris(2,2,6,6-tetramethyl- 3, 5-heptanedionate) bismuth, bis(2,4-didecylpentadienyl) fluorene, dicarbonyl pentadienyl hydrazine, hydrazine acetyl acetonate, (2,4-dimercapto pentadiene (钌) (cyclopentadienyl), bis(2,2,6,6-tetradecyl-3,5-heptanedionate) ruthenium (1,5-cyclooctadiene), (2,4 - Dimercapto pentadienyl) fluorenyl (fluorenylcyclopentadienyl), (1,5-cyclooctadiene) fluorene (cyclopentadienyl), (1,5-cyclooctadiene) fluorene (fluorenylcyclopentadienyl), (1,5-cyclooctadiene) fluorene (ethylcyclopentadienyl), (2,4-dimethylpentadienyl) fluorene (ethylcyclopentyl) Dienyl), (2,4-dimethylpentadienyl)anthracene (isopropylcyclopentadienyl), bis(indenyl, fluorenyl-dimethyltriphenyltetradecyldiimide) Acid) hydrazine (1,5-cyclooctadiene), bis(hydrazine, hydrazine-dimethyl1,3-dimethyldiimide) hydrazine (1,5-cyclooctadiene), double ( Allyl) hydrazine (1,5-cyclooctadiene), ( 76-C6H6) 钌(1,3-cyclohexadiene), bis(1,1-dimercapto-2-aminoethoxy)indole (1,5-cyclooctadiene), double (1, 1-Dimethyl-2-aminoethylamino acid) hydrazine (1,5-cyclooctadiene), and derivatives thereof, and mixtures thereof. 3. The method of claim 3, wherein the reducing gas comprises one or more gases selected from the group consisting of: hydrogen, ammonia, decane, two stone smoldering, two sub-stone shovel, methyl stone Xizhuan, ethyl zephyr, chlorite, dioxane, hexa-dioxane, borane, diborane, triborane, tetraborane, pentaborane, triethylborane, and combinations thereof a group of objects. 40. The method of claim 39, wherein the step of forming the 41 1376014 layer is performed between a temperature range of from about 200 ° C to about 4 ° C ° C. The method of claim 39, wherein the step of forming the layer of tantalum is carried out at a pressure of from about 0.1 Torr to about 80 Torr. 42. The method of claim 38, wherein the purge gas system is selected from the group consisting of helium, argon, hydrogen, nitrogen, and combinations thereof. 43. The method of claim 41, wherein the ruthenium containing compound is pulsed into the processing chamber for about 5 seconds to about 1.25 seconds. 44. The method of claim 43, wherein the reducing gas system enters the processing chamber in a pulsed manner for from about 1 second to about 2 seconds. 45. The method of claim 42, wherein the flushing gas system enters the processing chamber in a pulsed manner for from about 0.07 seconds to about one second. 4. The method of claim 39, wherein the enamel layer has a thickness of from about 10 angstroms to about 100 angstroms. The method of claim 39, wherein the ruthenium-containing compound is injected into the processing chamber in a sequential pulse manner. 48. The method of claim 47, wherein the ruthenium containing compound is delivered in a perpendicular manner relative to a plane of the substrate. 49. A method of forming a germanium layer on a substrate for an integrated circuit process, comprising the steps of: placing the substrate in a processing chamber; exposing the substrate to a double (2, 4) - dimethylpentadienyl) ruthenium to chemically adsorb a ruthenium containing layer on the substrate, wherein bis(2,4-dimercapto pentadienyl) oxime is coordinated via a gas having a central expansion channel System transporting; rinsing the processing chamber; exposing the ruthenium containing layer to a reagent; and reacting the reagent with the ruthenium containing layer to form the ruthenium layer on the substrate. 50. A method of forming a layer of germanium on a substrate for use in an integrated circuit process, comprising the steps of: placing the substrate in a processing chamber; via a gas distribution system having a central expansion channel Transmitting a reagent and a sequential pulse of a processing gas containing bis(2,4-dimethylpentadienyl) ruthenium; 43 1376014 rinsing the processing chamber between the reagent and the sequential pulse of the processing gas And reducing the bis(2,4-dimethylpentadienyl)anthracene to form the ruthenium layer on the substrate. 51. A method of forming a layer of tantalum on a substrate for use in an integrated circuit process, comprising at least the steps of: placing the substrate in a processing chamber; via having a central expansion channel a gas system for transporting a reagent and a sequential pulse comprising a treatment gas containing a ruthenium compound selected from the group consisting of tris(2,2,6,6-tetramethyl-3,5-heptanedionate) , bis(2,4-didecylpentadienyl) fluorene, dicarbonyl pentadienyl hydrazine, hydrazine acetyl acetonate, (2,4-dimercapto pentadienyl) fluorene (cyclopentadiene) (), bis(2,2,6,6-tetradecyl-3,5-heptanedionate) ruthenium (1,5-cyclooctadiene), (2,4-dimethylpentadienyl) ) fluorene (fluorenylcyclopentadienyl), (1,5-cyclooctadiene) fluorene (cyclopentadienyl), (1,5-cyclooctadiene) nail (methylcyclopentadienyl) ), (1,5-cyclooctadiene) fluorene (ethylcyclopentadienyl), (2,4-dimercapto pentadienyl) fluorene (ethylcyclopentadienyl), (2, 4-didecylpentadienyl) fluorene (isopropylcyclopentadienyl), bis(N,N-dimercapto1,3-1,3-diimide ) 钌 (1,5-cyclooctadiene), bis(N,N-dimercapto1,3-1,3-decyldiimide) hydrazine (1,5-cyclooctadiene), (7? 6-C6H6) 钌(1,3-cyclohexadiene), bis(allyl)indole (1,5-cyclooctadiene), bis(1,b dimethyl-2-aminoethoxy)钌(1,5-cyclooctadiene), bis(1,1-dimercapto-2-aminoethylamino) hydrazine (1,5-cyclooctadiene), and derivatives 44 thereof 1-376014 In the group consisting of the mixture thereof; rinsing the processing chamber between the reagent and the sequential pulses of the processing gas: and reducing the cerium-containing compound to form the ruthenium layer on the substrate. 45 Γ376014 柒, designated representative map: (1) The representative representative of the case is: Figure 2. (2) The symbol of the representative figure of this representative figure is a brief description: 80 chamber 137 upper part 82 chamber main body 138, 139 reactant gas; 84 side wall 140 flushing gas source 86 bottom 142A, B valve 88 slit valve 143 A , B gas distribution line 90 substrate 144A, B valve seat assembly 91 receiving surface 145A, B flushing line 92 support 146A, B valve seat assembly 114, 118 lifting motor 150A, B gas conduit 116 lifting plate 160 bottom surface 120 pin 166 Exhaust zone 122 Flushing ring 178 Vacuum system 124 Flushing channel 179 Venting channel 130 Gas distribution device 180 Control unit 132 Chamber cover 182 Central processing unit 134 Expansion channel 183 Control software 135 Lower part 184 Support circuit 136A, B Gas inlet 186 Memory 捌, if there is a chemical formula in this case, please reveal the most characteristic chemical formula.